09 Aromatic Compounds 13th CC (E) - WA 1 PDF

ORGANIC CHEMISTRY
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CRASH COURSE
AROMATIC
COMPOUNDS
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AROMATIC COMPOUNDS
MAIN SOURCE
Bituminous coal when subjected to destructive distillation in the absence of air [1000º–1200ºC] the
chief constituent obtained is coal tar.
Fractional distillation of coal tar : Different fractions are :
Fraction Temperature Main constituents

(a) Light oil 80 – 170ºC Benzene, toluene, xylene etc.
(b) Middle oil (carbolic oil) 170º – 230ºC Naphthalene,
Phenol etc.
(c) Heavyoil 230º 270ºC Cresols, naphthalene
(d) Green oil 270º – 360ºC Anthracene
(e) Pitch Residue Carbon
BENZENE
[i] Discoverer : Michael Faraday [ii] C–hybridisation : sp2

[iii] Geometry– Hexagonal [iv] Bond angle : 120º
[v] C–C Bond length : 1.39Å [vi] C–H Bond length : 1.09 Å
[vii] Resonance in bezene :
[ix] Number of angles of 120º : 18

[x] Localized and delocalized –orbital
Localized –orbital Localized –orbital
2 3 2 3
1 4 1 4
6 5
6
5
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Obviously, each orbital formed in the partial overlapping is attracted by two carbon nucleus hence less
stable.
Delocalized p-orbital :
Methods of Preparation of Benzene :

Isolation From ‘Light Oil Fraction – Industrial method :
In ‘light oil’, at least 60–65% benzene is present.Alkaline impurities (aniline, pyridine, quinolene, etc.)
are removed by washing ‘light oil’ with cold and conc. H2SO4. The acidic impurities are removed by
washing with dilute NaOH solution.After that, NaOH is removed by washing with water.Three fractions
are obtained at different temperature ranges by fractional distillation of the neutral sample of oil.
[i] 90% Benzol (90’s benzol). 80–110º [ii] 50% Benzol (50’s benzol). 110–140º
[iii] Solvent naphtha – 140º–170º
The 90% benzol contains about 70% benzene 24% toluene and remaining xylenes. Fractional distillation
gives benzene at 80º, toluene at 110º and a mixture of all the three xylenes at 137–145º. Crystals are
formed on cooling benzene from which pure benzene can be obtained by melting the crystals.
ELECTROPHILIC AROMATIC SUBSTITUTION (EAS)
Based on its structure and properties, what kind of reaction should benzene undergo ? Are any of its
bond particularly weak does it have electron rich or electron deficient atom.
* Benzene has six p-electron delocalized in six p-orbitals that overlap above and below the plane of ring.
These loosely held -electron make the benzene ring electron rich, and so it reacts with electrophile.
* Because benzene six -electron satisfy Huckel’s rule, benzene is especially stable. Reactions that keep
the aromatic ring intact are therefore, favoured.
* Electron cloud above and below the plane of benzene shields the ring carbon from the attack of a
nucleophile.
As a result, the characteristic reaction of benzene is electrophilic aromatic substitution - a hydrogen

atom is replaced by an electrophile.
H E 
+ E +H
electrophile
Substitution of H by E
Benzene does not undergo addition reaction like other unsaturated hydrocarbons, because addition
would yield a product that is not aromatic . Substitution of a hydrogen on the other hand, keeps the
aromatic ring intact.
H H E
Addition + Cl2
Cl
; Substitution E
X
Cl
H
Product is not aromatic Product is aromatic
THE GENERAL MECHANISM OF EAS
EAS reactions occur via a two steps mechanism.
Step 1. Addition of the electrophile
H H  H +
H H
E E E E E
Slow   + +
(–complex)
Step 2. Loss of a proton to reform the aromatic ring

H B E
E Fast
+B–H

Any of the three resonance structures of the carbocation intermediate can be used to draw the product.
The energy changes in EAS are shown in figure. The mechanisms consist of two steps, so energy dia-
gram has two energy barriers. Because the first step is rate-determine, its transition state is higher in
energy.
Transition state
step-1
Transition state
step-2
+
H
E
+ +
(–complex)
Energy
H E
 
+E +H
Reaction co-ordinate
Most examples of EAS proceed by this sequence of events :
1. Generation of an electrophile
2. Attack of he aromatic ring on the electrophile
3. The resulting carbocation is stabilized by the resonance
4.Aproton is elimination from the carbocation
5. Asubstituted aromatic compound is formed
NITRATION OF BENZENE
The introduction of a nitro (–NO2) group on benzene known as nitration of benzene. The most common
reagent for the nitration of aromatic compound is mixture of concentration HNO3 and concentration
H2SO4 (mixed acid).

The electrophile required for the nitration is nitronium ion (–NO 2) .
HNO3 + H2SO4 NO2
or Mixed acid

Mechanism : H2SO4  H + HSO4
O O O
N H  N –H2O 
N or NO2

O OH O OH2 O

 H 
NO 2 HSO 4 NO 2
NO 2

Besides mixed acid, other reagents have also been used for nitration such as nitronium salts
       
(NO 2Cl, NO 2F, NO 2,ClO 4, NO 2,SO 3)

In the case of fuming HNO3 alone NO2 is formed as follow
 
2HNO3  NO2 + NO3 + H2O

In nonpolar solvent N2O5 get dissociated and produces NO2
 
N2O5  NO2 + NO3
Problem : Compare rate of nitration among C6H6, C6D6 and C6T6.

Solution : C6H6 = C6D6 = C6T6
Therefore nitration of benzene does not shows primary kinetic isotopic effect.
HALOGENATION OF BENZENE
The introduction of halo (–X) group on benzene known as halogenation of benzene

Br Br
FeBr 3 AlCl 3
+ Br2 + HBr ; + Br2 + H–Br
The bromination or chlorination of benzene requires a Lewis acid catalyst such as FeBr3,AlBr3, FeCl3or
AlCl3.
Sometime Fe or Al is used but real catalyst is not Fe or Al itself but FeX3 or AlX3 is formed from the
reaction between halogen and Fe orAl.
Mechanisms for Bromination

   
Br – Br + FeBr3 Br – Br – FeBr Br + FeBr
(Bromonium ion)
 H 
Br Br
Br Br – FeBr
+ HBr + FeBr3

Mechanisms for Chlorination

   
Cl – Cl + AlCl3 Cl – Cl – AlCl3 Cl + AlCl4
(Chloronium ion)
 H  Cl
Cl Cl Cl – AlCl3
+ AlCl3

   
Bromination and chlorination also occur by HOBr and HOCl , obtained by reaction between H2O and
X2.
H2O + X2  2HOX (X = Cl, Br)
Iodination of benzene requires an acidic oxidizing agent such as nitric acid. Nitric acid is consumed in the
reaction, so it is a reagent rather a catalyst.
I
1 I + HNO + NO2 + H2O
+ 2 3
2
Mechanisms for Iodination


HNO3 + 1 I2 I + NO2 + OH
2
 H  I
I I OH

The electrophile required for halogenation reaction is halonium ion ( X )
Sulphonation of Benzene
Sulphonation is usuallydone with concentration H2SO4. Electrophile required for sulphonation reaction
is SO3.
SO3H
Conc. H2SO4
Benzene sulphonic acid
Mechanisms :

H 2SO 4  H + HSO 4
O O O
H  –H
HO – S – OH HO – S – OH S
O O
O
H  SO3 SO3H
S SO3 HSO4 H
+
O O 
Fuming sulphuric acid or oleum (H2S2O7) is also used to sulphonate aromatic ring.
H 2S2O 7 SO 3H
SO 3 + H2SO4
Mechanisms :
O
H  H  SO3H
S SO3 H2SO4 SO3H HSO4
+ –HSO4 
O O 
Sulphonation of benzene is a reversible reaction. If benzenesulfonic acid is heated in dilute acid, the
reaction proceed in reverse direction.
SO3H
H/H 2O, 100ºC
+ SO3 + H 
Mechanisms of desulphonation
SO 3H SO 3H

+ H  H + SO 3H

Due to reversibility in reaction shows kinetic isotopic effect. Rate of reaction  C–H > C–D > C–T
RELATIVE REACTIVITY OF SUBSTITUTED BENZENE
Ortho para directors Meta directors

Strongly activating Moderately deactivating
O O O O O O

–O, –NH 2, – NR2, – OH, – OR – C – H, – C –, – C – Cl, – C – NH 2, – C – OH, – C – OR
Moderatelyactivating Stronglydeactivating
O O
 
– NH – C – CH 3, – O – C – CH 3 – NH3, – NR3 , – NO2 , – C  N, – CF3, – CCl3
Weakly activating
–CH3, –CH2CH3, – R
, – CH = CH 2
Weakly deactivating
– F , –Cl , – Br , – I
AROMATIC HYDROCARBONS
CH3 CH3 CH3 CH3 CH= CH2 CH(CH3)2

CH3
CH3
Benzene Benzene o–xylene m–xylene CH3 styrene cumene
(1, 2–) (1, 3–) p–xylene
(1, 4–)
CH3
CH2
H3C CH3
biphenyl biphenyl naphthalene anthracene phenanthrene 1, 3, 5-trimethylbenzene
(phenylbenzene) (phenylbenzene) (mesitylene)
Source
(a) Fractional distillation of Coaltar
The dark-brown sticky liquid called coal-tar is a mixture of several aromatic hydrocarbons, phenols,
bases etc. The first step in the separation of coal-tar into its components is distillation in a fractionating
column as given in table.
(b) High temperature cracking

Petroleum (kerosene and low boiling fractions) cracking
  mixture of alkenes and alkanes.
cyclisatio
   aromatic hydrocarbon
n / aromatisat ion
CH2
HC CH2
+
HC CH2 –H2
CH2
Pt-Al2O3, Pt-Al2O3
–H2 –H2
Pt-Al2O3, Pt-Al2O3
–H2 –H2
(c) Polymerisation
3CH  CH red-hot tube

1870-2070 K
CH3
red-hot tube
2CH  CH + CH3C  CH
1870-2070 K
CH3
red-hot tube (o, p-also)

2CH3C  CH + CH  CH
CH3
CH3
red-hot tube
3HC  CCH3
H3C CH3
(d) Alkyl benzene synthesis

AlCl3, HCl
+ CH2 = CH2
368 K, Pressure
CH (CH3)2
H3PO4
+ CH2 = CHCH3
523 K, pressure
(e) Friedel-Crafts reaction

CH2CH3
(i) AlCl3
+ CH3CH2Cl + HCl
(ii) H2O
(f) Decarboxylation of Aromatic acids

, CaO
COONa + NaOH + Na2CO3
(g) Wurtz-Fitting reaction
dry ether
Br + 2Na + Br – R R + 2NaBr
(h) Deoxygenation of Phenols

Zn ; Zn
OH OH CH3
 
CH3
(i) Reduction of Diazonium salts

N2Cl + H3PO2 + H2 O + N2Cl + H3PO2 + HCl
(j) Desulphonation of sulphonic acids

400 – 420 K
SO3H + H2O + H2SO2
steam HCl, high pressure
Mechanisms of the above reactions have been given in further section.
1. All meta-directing groups are deactivating groups;

2. All ortho, para-directing groups except for the halogen are activating groups.
3. The halogens are deactivating groups
The activating substituents make the benzene ring more reactive towards electrophilic substitution, the
deactivating substituents make the benzene ring less reactive towards electrophilic substitution.
All the strong activating substituents donate electrons into the ring by resonance and withdraw electrons
inductively. The fact that they are strong activators indicate that electron donation into the ring by
resonance (which increases electron-densityhence, nucleophilicity)is much greater thanelectron withdrawl
from the ring by the inductive effect (which decreases electron-density hence nucleophilicity). Strongly
activating substituents are :
NH 2 OH OR
The moderately activating substituents also donate electrons into the ring by resonance and withdraw
electrons from the ring inductively. However they donate electrons into the ring by resonance less
effectivelythan do not strongly activating substituents. These substituents are less effective at resonance
donation since, they can donate electrons by resonance in two competing directions- into the ring and
away from the ring and thus net resonance effect is diminished and still electron donation by resonance
is more than the electron withdrawl by induction and thus, these substituents are activators though
moderately.
O O O O O
  
HNCCH3 HNCCH3 HNCCH3 HNCCH3 HNCCH3
 
(substituents donates electrons by resonance into the benzene ring)
O O

HN–CCH3 HN = CCH3
(substituents donates electrons aways from the benzene ring)

Alkyl, aryl and CH = CHR groups are weakly activating substituents. Two of the three groups (aryl and
CH = CHR) can donate electrons into the ring by resonance and can also withdraw from the ring by
resonance. The fact that they are weak activators indicates that they are slightly more electron-donating
than they are electron-withdrawing . An alkyl substituent is a weak electron donor because of
hyperconjugation.
R CH = CH/R
The halogen are weakly deactivating substituents. They donate electrons into the ring by resonance and
withdraw electrons inductively. Since, they have been found deactivators, we can conclude that they
withdraw electrons inductively more strongly than they donate electrons by resonance.
Cl Cl

The moderately deactivating substituents all have carbonyl groups directly attached to the benzene ring.
They withdraw electron both inductively and by resonance.
O O O
CH CR COR
The strongly deactivating substituents are powerful electron withdrawers. With the exception of
   
– NH 3, – NH 2 R, – NHR 2, and – NR 3 and they withdraw electrons both inductively and by resonance. The
ammonium ions have no resonance effect, but the positive charge on the nitrogen atom causes them to
strongly withdraw electron inductively.
O 
O  O 
O = S – OH N CN NR3
(a) Catalytic hydrogenation
+ 3H2 Pt
CH3 CH3
+ 3H2 Pt
Birch reduction :
Treatment of areanes with group Imetal (like sodium, lithium) and methanol (or ethanol) in liquid reduces
arenes to non-conjugated dienes.
H H
Na, liquid NH 3
CH3OH
H H
1, 4-cyclohexadienes
Alkyl substituted arenes give 1, 4-cyclohexadienes in which the alkyl group is a substituent on the double
bond.
CH3 CH3 CH3
Na, liquid NH3
rather than
CH3OH
Metal ammonia -alcohol reduction of aromatic ring is known as Birch reduction and is one type of a
more general class of reactions called dissolving metal reduction.
(b) Addition of Halogen
Cl
Cl Cl
+ 3Cl2 UV
Cl Cl
Cl
benzenehexachloride, B.H.C, 666
Benzenehexachloride (BHC, C6H6Cl6) is also called Lindane or Gammaxene (-isomer) and is used
insecticide.
(c) Ozonolysis
CHO
Zn/H2O
+ 3O3
CHO
glyoxal
(d) Oxidation
CHO
Zn/H2O
+ 3O3
CHO
glyoxal
O2 CHOOH  CHCO
3 O
v2o5 , 770 K CHCOOH CHCO
maleic acid maleic anhydride
COOH
O2  CO
O
v2o5, 770 K CO
COOH
phthalic acid phthalic anhydride
CH3 COOH
KMnO4/OH¯

When oxidised using KMnO4/OH¯, Na2Cr2O7/H+, KMnO4/H+ the entire side chain, with at least one
H at -C, regardless of length is oxidised to –COOH.
CH (CH3)2 COOH
KMnO4/OH¯

The conversion of alkyl benzenes to benzoic acid with strong oxidations suggest that benzene ring is
more stable than the side chains; this is correct so long as the side-chain contains at least one benzylic
C–H bond. The first step in the mechanism is the removal of hydrogen from the benzylic carbon. If the
side-chain has no C–H bond at the -carbon (w.r.t. benzene nucleus), then benzene ring is cleaved.
CH3 CH3
Na2Cr2O7
– C – CH3 HOOC – C – CH3 CH3COOH
H2SO4
CH3 high temp. CH3
(–C)
CH3 CH(OOCCH3)2 CHO


CrO3, acetic anhydride H3O
CH(OCrCl2OH)2

CrO2Cl2 H3O
(Etard)
(e) Combustion
2C6H6 + 15O2  12CO2 + 6H2
(f) Side-chain halogenation
CH3 CH2Cl CHCl2 CCl3
boiling Cl2 Cl2
+ Cl2
benzyl chloride benzal chloride benzotrichloride
This provides a source of preparing other derivatives from benzene and toluene.
CH3 CH3 CCl3
, CH3Cl, AlCl3 3Cl2

boiling +
Cl2, boiling 2Cl2, boiling (i) KOH, (ii) H3O
CH2Cl CHCl2 COOH
+
aq. KOH NH3 KCN, H3O aq. KOH
CH2OH CH2NH2 CH2COOH CHO
NBS, benzoyl peroxide

CH3 CH2Br
CCl4, 350 K
(NBS is N-bromo succinimide)
DIRECTING INFLUENCE AS DECIDED BY ELECTRON DENSITY
• –OH group is ortho and para-directing since it increase electron-density at ortho and para-positions
for electrophilic attacks; electron-density at meta-position is decreased hence, electrophilic attack at
this position is least.
O–H O – H O – H O – H O–H
 
I II III IV V
1 to V are different resonance structures and VI resonance hybrid structure.


+
OH

–

–
Electrophile can attack the sites with increased
electron density which are ortho para w.r.t. –OH group

–
VI
Naturally nucleophile cannot attack ortho and para-sites but can attack at meta-site (but less reactive)

+
OH

–

–
Nucleophile can attack meta-sites

–
• –NO2 group is electron-withdrawing group. It deactivates ortho and para-position for electrophilic
attack and thus electrophile can occupy meta-position. I to V are resonance and VI is resonance hybrid.
       
O  O O  O O  O O  O O  O
N N N N N
 
I II I II IV V
 –
O O
N
 
+ +
Electrophile cannot attack ortho and para-sites since,
they are electron-deficient centres but meta-site

+
with less reactivity.
In this case nucleophilic attack at electron-rich ortho and para-sites is favoured.

NO2
 +
+ Nucleophile can attack here
+
ANAMALOUS BEHAVIOUR OF HALOGEN SUBSTITUENT
– X(F, Cl, Br, I) is o–, p-directing but is deactivating group.

X X X X X X+
 
–

–


–

This deactivating nature is attributed to high electronegativitity of the halogen atom due to which they
withdraw electrons; resonance effect explains its electron-donating behavivour.
X+ X+
   
– – – –
–I > +M
 
– –
electron displacement overall result; o–,

due to inductive effect not p-directing but
compensated by resonance deactivating
effect
Alkyl groups and Orientation
Alkyl groups (–CH3, –CH2CH3, etc.) have complete octet and are without one-pair of electrons; but
they are ring activators and o-, p-directors. They not only show electron-pumping effect, but also when
attached to conjugated system show hyperconjugated effect (no-bond resonance). This type of reso-
nance requires the interaction of -electrons instead of usual lone-pair of electrons. In toluene,
hyperconjugation is shown below :
H H H H H H
  
H–C–H H C–H H C–H H C–H H–C–H H C–H
+
 – –

 –
resonance hybrid
Thus, hyperconjugation helps in increasing-density at o-and p-sites in case of alkyl groups.

There must be at least one H-atom on the carbon of the alkyl group joined to the ring carbon to take
part in hyperconjugation and relative ability of alkyl groups for this effect is
methyl > 1º > 2º > 3º
C(CH3)3 C(CH3)3
+
+ NO2
NO2
In this case, only p-isomer is obtained. It is due to steric influence of the substituents –C(CH3)3 and due
to its unabilityto show hyperconjugation.
Orientation and Synthesis

By using the nature of directing group (subtituent), it is possible to prepare variety of products.
To prepare meta-bromo nitrobenzene from benzene, we have to first carry out nitration and then bromi-
nation; and to prepare o-and p-dereivatives, sequence will be bromination and then nitration.
Br NO2 NO2
Br2, Fe HNO3/H2SO4 Br2, Fe
Br
(Br is o-, p-directing) (–NO2 group m-
is m-directing)
Br Br
HNO3 NO2
+
H2SO4
NO2
o- p-
Orientation in Disubstituted benzene

When two substitution are present, orientation of the third coming SE is complicated.
–CH3 group is o–, p-directing and –NO2 group is m-directing, thus in p-nitrotoluene, new electrophile
can be in a position shown by arrow :
CH3
meta w.r.t. – NO2
NO2 ortho w.r.t. – CH3
Similarly we can decide the position of the new electrophile in other disubstituted compounds.
SO3H NHCOCH3
CN
NO2 NO2
both meta-directing – NHCOCH3 ortho, para and
– CN meta-directing
Problems may arise in the following cases :

OH Strongly activating
CH3 Weakly activating
Both are ortho, para-directing and none of the vacant positions are ortho-and para, w.r.t. each. In such
cases we follows : (a) Strongly activating groups generally win over deactivating or weakly activating
groups.
OH OH
HNO3/H2SO4 NO2
– NO2 is ortho w.r.t. – OH (Strongly activating)
CH3 CH3
activating
OH OH
Br2, Fe
CHO CHO
deactivating Br
weakly activating OH OH CH3

HNO3, H2SO4 NO2
+
NO2
deactiving Cl Cl Cl
(b) If the subtitution are meta to each other, SE in between vacant sites takes place rarely.
Cl Cl Cl Cl
Br Br
Br2, Fe
+ +
Br Br Br Br
Br
1% 62% 37%
HALOGEN COMPOUND
Aryl Halides
Source/Preparation
• Direct halogenation :
Cl Cl Cl
Cl
Fe Fe/Cl2
+ Cl2 +
Cl
Low temperature and the presence of a halogen carrier favour nuclear substitution. The chlorides or
bromides of Al, Fe, Sb may use used :
Cl2 Cl2 +
Fe FeCl2 FeCl4¯ + Cl
 H
 Cl
+ Cl
-complex
(stable by resonance)
 H H H H
Cl Cl Cl + Cl
  
 H Cl
+
Cl +H
+
FeCl4¯ + H FeCl3 + HCl
Iron is most commonly used being converted to Lewis acid FeCl3 as shown above.
It is again SE reaction and without halogen-carrier (Lewis acid), Cl+ (halonium) is not formed and hence,
reaction is not possible :
CH3 CH3 CH3

Fe Br
+ Br2 +
toluene
Br
o– p–
bromotoluene
A methoxy group is so strongly activating that anisole quickly bromines in water without a catalyst :
OCH3 OCH3
Br2 Br Br
H2O + HBr
Br
Direction iodination is not possible since, iodine is least reactive and HI formed makes reaction revers-
ible. In presence of oxidising agents like HNO3 or HIO3, iodination of benzene is possible and HI
formed is converted to I2 :
[O]
1/2 I2 + HNO3 + I + H2O + NO2
5 HI + HIO3 3 I2 + 3H2O
Iodination probably involves an electrophilic aromatic subtitution with iodonium (I+) acting as the
electrophile. I+ is formed from iodine by oxidation with HNO3.
H+ + HNO3 + 1/2 I2  I+ + NO2 + H2O

COOAg + Br2 Br + AgBr + CO2 (Hunsdiecker reaction)
CCl4
Diazonium salts are converted to halogen compounds :

+
Br N2 Cl¯ Cl
CuBr/HBr CuCl/HCl
N2 + + N2
(Sandmeyer) (Sandmeyer)
+ +
N2 X¯ N2 BF4¯ F
HBF4 
+ N2 + BF3
(Sandmeyer)
N2Cl I

+ KI (Gattermann) + KCl + N2
Diazonium salts are obtained by diazotisation of amino compounds and this provides a better route to
convert amino compounds into halogen compounds :
+
NO2 NH2 diazotisation N2 Cl¯ Cl
Sn/HCl NaNO2 + HCl CuCl/HCl
Reduction 273 K SN
CH3 CH3 CH3 CH3
CuCl Cl + H 2O (Raschig process)

+ HCl + 1/2 O2
Side-Chain Derivatives
CH3 CH2Cl CHCl2 CCl3

Cl2 Cl2 Cl2
high temp;
light
(boiling) benzyl benzal benzotri
chloride chloride chloride
Side-chain halogenation involves free radical mechanisms due to lower bond energy of the benzyl C–H
bond :
•
CH3 CH2
+ Cl• + HCl
stable benzyl free radical
Benzyl radical is stabilised by resonance due to delocalisaton of odd electrons into ring :
•CH2 CH2 CH2 CH2 •CH2
• •
•
NBS can also be used for bromination of side-chain alkyl group :
NBS
CH2CH3 CH – CH3
Br
(by allylic subtitution)
In presence of an activating group – OH or – NH2, side chain halogenation is difficult :

CH3 CH3
+ Br2
Br Br
OH OH
Properties
Physical
• Less polar, insoluble in water but soluble in organic solvents like ethanol and ether.
• They show physiological activity and are used as insecticides. Examples are :
CCl3
Cl
CH
Cl
(dichlorobenzene) (DDT)
Chemical
(a) Low reactivity of Aryl halide for SN reaction
C–X bond in aryl halide is stable due to delocalisation of electrons by resonance. Also (C–X) bond
possesses a double bond character like vinyl chloride and is stronger than C–X bond in alkyl halide.
Cl Cl Cl Cl Cl Cl+

strong
 – –
 Nu no reaction
–

Nu – C – Nu + X
while – C – X
weak weak
Hence, SN reaction is not possible in benzene nucleus under ordinary conditions. However, under high
temperature and pressure, SN reaction is made possible.
570 K, pressure
+ OH¯ OH + Cl¯
CuCN
Cl + CN¯ CN + Cl¯
470 K, pressure
aq. NH3
+ NH3 + Cu2O NH2 + CuCl + H2 O
470 K, pressure
If the benzene ring has (1) one or more substituents that strongly withdraw electrons from the ring by
resonance, and (2) a good leaving group (such as halogens), nucleophilic aromatic substitution reac-
tions can occur without using extreme conditions. These electron-withdrawing groups must be posi-
tioned ortho or para to the leaving group. The greater the number of electron-withdrawing substituents,
the easier it will be to carryout the nucleophilic aromatic substitution reactions.
Cl
Z Cl G withdraws electron
+z: stabilies carbanian,
activates, SN reaction
G G is made favourable

G = – N (CH3)3, – NO2, – CN, – SO3H, – COOH, – CHO
O2 N Cl + OH¯ 430 K O2 N OH
O2 N Cl + OH¯ 370 K O2 N OH
NO2 NO2
NO2 NO2
O2N Cl + H2O warm O2N OH
NO2 NO2
Cl
Z Cl G releases electrons destabilises
+z: carbanion, deactivates
G = – NH2, –OH, –OR, –R
G G
Nucleophilic aromatic substitution takes place by a two-step reaction known as an SN Ar reaction by

following mechanisms :
X X Y X Y X Y X Y
+Y 
 
nucleophile
(slow) 
NO2  N  N  N  N
O  O O O

O
 O  O  O
Y
fast + X
NO2
(b) Elimination-Addition Through Benzyne Intermediate
An aryl halide can undergo a nucleophilic substitutoin reaction in the presence of a verystrong base such
as NH 2 .
When chlorobenzene – that has the carbon to which chlorine is attached isotopically labelled with 14C
– is treated with amide ion in liquid ammonia, aniline is obtained as a product. Half of the product has the
amino group attached to the isotopically labelled carbon (*) as expected, but the other half has the
amino group attached to the carbon adjacent to the labelled carbon.
Cl NH2
* * * NH2
 NH3 (liquid)
+ NH2 +
(approximately in equal amounts)
The mechanisms that accounts for the experimental observations involves formation of a benzene inter-
mediate which has two equivalent carbon atoms to which amino group can be attached. Benzyne has an
extra -bond between two adjacent carbon atoms of benzene and can be formed as :
Mechanism :
•• ••
NH2 NH2
•• * • 
attack at C* •
• H – NH2 • ••
+ • NH
• 2
Cl
(labelled)
14
H 
NH2
–NH3
–Cl¯  •• ••
*• • NH2 •• * NH2 
attack at C H – NH2 ••
+ •• NH2
(unlabelled)
Substitution at the carbon (*) that was attached to the leaving group is called direct substitution. Substi-
tution at the adjacent carbon is called cine substitution.
CH3 CH3 CH3
Br NH2
liquid NH3
+ NaNH2 +
NH2
o-bromotoluene
o-toluidine m-toluidine
(by direct substitution) (by cine substitution)
(c) Wurtz-Fitting Reaction
Cl + CH3Cl + 2Na ether CH3

aryl halide alkyl halide
ether CH2
CH2Cl + Cl + 2Na
alkyl halide alkyl halide

(side chain)
If only aryl halide is involved, diphenyl is formed (Fitting reaction)

(d) Ullman synthesis
2 I + 2Cu
(e) Reaction with Chloral

DDT is formed when chloral reacts with chlorobenzene in presence of concentrated H2SO4.
Cl
Cl
conc. H2SO4
2 Cl + H – C = O Cl C – C – Cl
CCl3 H Cl
2, 2-di (p-chlorophenyl)-1, 1
1-trichloroethane (DDT)
DDT is causing ecological problems, its use as insecticides is being banned.

Nitration
Cl Cl Cl
conc. HNO3 NO2
+ chloro nitrobenzene
conc. H 2SO 4
NO2
o- p-
Chlorination
Cl Cl Cl
Cl
Cl2, Fe
+ dichlorobenzene
Cl
o- p-
Sulphonation
Cl Cl Cl
SO3H
H2SO4
+ chlorosulphonic acid
SO3H
o- p-
• Chlorine is not a good donor of electrons by resonance due to its high electronegativity. Thus, the
inductive effect of the Cl atom overcomes the resonance effect, and thus, it deactivates the benzene ring.
(g) Substitution on benzyl carbon (SN) : The greater reactivities of benzylic halides result from the stabili-
ties of the carbocation intermediates that are formed when they react.
 
CH2 – Cl CH2 Cl
  
CH2 CH2 CH2 CH2 CH2
 
Tertiary cumyl chloride ionises to a carbocation with four important resonance structure :
CH3 CH3
C – Cl C  Cl 
CH3 CH3
CH3
CH3
C C
 CH3
CH3
(resonance-stablised)
Because of the possibilitie of resonance, ortho and para substituent group on the benzene ring that
activate electrophilic aromatic substitution further accelerate SN 1 reaction at the benzylic position. Thus
p-methoxy tert-cumyl chloride (I) undergoes hydrolysis about 3400 times faster than tert-cumyl chlo-
ride II.
CH3 CH3
CH3O C – Cl C – Cl
CH3 CH3
I II
Benzylic halides undergo SN reactions like aliphatic halides.
aq. KOH
CH2 – Cl CH2OH
KCN
CH2CN
NH3/NaNH2
CH2NH2
This provides a path of converting toluence into so many other compounds benzyl chloride.
Aromatic Nitro Compounds
CH3
NO2 NO2 O2N NO2
NO2 CH2NO2
NO2 O2N NO2

NO2
nitrobenzene m-dinitrobenzene phenylnitromethane 1,3,5-trinitrobenzene 2,4,6-trinitrotoluene
Source
• Direct nitration
Nitrating agent is
(a) conc. HNO3 + conc. H2SO4 or (b) acetyl nitrate (N2O5 in acetic anhydride)
– NO2 is deactivating group, hence, further nitration takes place with fuming HNO3 and H2SO4 mixture.
Intermediate is o-complex (arenium carbocation) stabilished by resonance.
NO2 NO2
conc. H2SO 4 fuming HNO 3
+ HNO3
conc. 330 K conc. H2SO4 NO2
+ + –
OH – NO 2 + 2H 2SO 4  OH 2 + H 3O + 2HSO 4
nitronium ion
 H H H H
NO2+ NO 2 NO2 NO2 NO2
+
 
-complex resonance hybrid
 H NO2
NO2 +
+H
CH3 CH3 CH3
+ NO2
NO 2
+
300 K
NO2
o-nitrotoluene p-nitrotoluene
• –CH3 and – OCH3 groups are activating groups hence, nitration of toluene and methoxy benzene
(anisole) is easier than that of benzene.
CH3 CH3
NO 2
+ CH 3CO – O – NO 2 + CH 3COOH
acetyl nitrate
toluene toluene
(CH 3CO) 2O +N 2O 5
acetic anhydride
OCH 3 OCH 3
NO 2
N2O5, (CH3CO)2O
+ CH 3COOH
methoxybenzene
• From Diazonium salts :
+ HNO 2, Cu 2O
H 3C N 2 Cl¯ H 3C N 2+ HCl + NO 2
• Oxidation ofAmino compounds : (using trifluroperbenzoic acid)

NH2 NHCOCH3
CH3COCl
acetylation to
protecting ring
NHCOCH3 NHCOCH3 NHCOCH3

HNO3 NO2
+
NO2
o– p–
N2BF4 NH2 NH2

NO2 NO2
NaNO2 + HBF4
and
o- (and p-) NO2

NaNO2 H2SO5
Cu,  (Caro's acid)
NO2 NO2 NO
NO2 HNO3/H2O2
NO2 NO2
o-dinitrobenzene p-dinitrobenzene
and (p-)
Properties
• Nitro-compounds are yellow crystalline solids (nitrobenzene is yellow liquid)
• Steam-volatile, denser than water in which they are in soluble.
• Nitro group is attacked by Grignard reagent; nitro-substituted aryl halides cannot be used for the
preparation of these reagents.
Mg/ether
O 2N Br X
There is also partial positive charge on the ortho and para-positions . Thus, –NO2 activates the benzene
nucleus for nucleophilic substitution at the ortho and para-positions.
O  O ¯
N
 
+ +
(nucleophile can attack here)


+
Electrophilic substitution (SE)

NO2 NO2
fuming HNO3/H 2SO4

NO2
m-dinitrobenzene
Further nitration to form trinitrobenzene takes place under drasitic conditions. Presence of electron-
releasing group activates benzene nucleus for SE .Toluene can be nitrated only once but nitro group
introduced retards a second nitration on the same ring.
CH3 CH3 CH3

NO2 conc. HNO /H SO NO2 conc. HNO /H SO O2N NO2
3 2 4 3 2 4
343 K 393 K
NO2 NO2
2, 4-dinitrotoluene 2, 4, 6-trinitrotoluene
NO2 NO2
Br2/Fe
Br
m-bromonitrobenzene
AROMATIC SULPHONIC ACIDS
They are derivatives of aromatic hydrocarbons in which one or more hydrogen of the benzene ring have
been replaced by the function – SO3H, called the sulphonic group.
SO3H SO3H
SO3H
NO2
CH3
benzene p-toluene m-nitrobenzene
sulphonic acid sulphonic acid sulphonic acid
SO2Cl CH3
O O
S – OH O – S – OH
O O
SO2Cl
benzene sulphonic acid a sulphate (an ester) benzene sulphonyl chloride p-toluene sulphonyl chloride
(carbon bonded to sulphur) (carbon bonded to oxygen) (Hinsberg's reagent) (IsCl)
(tosy chloride)
Source
• Direct sulphonation :
SO3H
SO3
+ H2SO4
conc. 300-330 K
CH3 CH3
SO3
+ H2SO4 + o-isomer
273 K
SO3H
(main)
In the sulphonation, electrophile is SO3 formed as :

2H2SO4  SO3 + H3O+ + HSO4¯
Although it appears neutral, sulphur carries positive charge due to resonance :

O O O
 
S S  S
O O O O O O
 H H H
SO3 SO SO SO
3 3 3
 
H
 SO
3
 H SO
3
SO 
3 + HSO4 + H2SO4
SO
3 SO3H
+ H3SO+ + H2O
Properties
• Colourless crystalline deliquescent solid.
• Very soluble in water and solution is stronly acidic.
+
SO 3H + H 2O SO 3¯ + H 3O
They are stronger acid than carboxylic acid.

SO2H COOH
–5
(Ka = very large) (Ka = 6.3 × 10 )
• Desulphonation :
The knocking out of sulphonic acid group from benzene nucleus is called desulphonation.
SO3H H
H SO3H
H+ 
 + SO3H
X
SO3 H + OH¯ (from water) H2SO4
The desulphonation is very useful for preparation of certain isomers which are otherwise not obtained in
pure state.
Reactions of sodium salt of benzene sulphonic acid :
(conversion into other derivatives)
SO3Na OH ONa OH
+
NaOH NaOH H
fuse
SH SO3Na NH2
NaSH, fuse NaSH, fuse
thiophenol
Source
(a) Nitrobenzene can be reduced under different media to produce aniline and related compounds.
Sn/HCl
NO 2 NH 2+ H 2O
NO2 NH2
(b) + 3 NH4HS + 3 NH3+ 3S + 2H2O

NO2 NO2
NH4 HS is suitable reagent where only one – NO2 (in stages) is to be reduced.
Cu2O
(c) Cl + NH3 NH2 + HCl
pressure, 437 K
C–Cl bond is stable, hence ammonolysis of aryl halide takes place under high temperature and pres-
sure. However electron withdrawing group in benzene nucleus makes C–Cl bond highly reactive.
NO2 NO2
NH3
O2N Cl O2N NH2
NO2 NO2
ZnCl2
OH + NH3 573 K NH2 + H2O
O
Br2/aq. NaOH, 
(d) CNH2
Hofmann degradation
NH2
When the migrating group is aryl, the rate of the Hofmann degradation reaction is increased by the
presence of electron releasing substituens in the aromatic ring.
G CONH2 OBr¯ G NH2
G : = – OCH3 > – H > – Cl > – NH 2
N3H,  (Schmidt)
(e) COOH NH2+ CO2 + N2
conc. H2SO4
H2, Ni
(f) N=N NH – NH
313 K, 15 atm
azobenzene hydrazobenzene
H2, Ni
313 K, 15 atm.
NH2
FeCl3
(g) + NH 2OH NH 2+ H 2O
hydroxylamine
CH3 CH3
CH3 – N HCl NHHCl NH2HCl NH2
CH3 CH3
  OH¯
(h)
N, N-dimethyl CH3 CH3 CH3
aniline hydrochloride
This is called Hofmann-Martius rearrangement and alkyl group preferentiallymigrates to p-position and
if it is occupied , then to o-position.
reduction
(i) NC NHCH3
2º
(N-methyl aniline)
R
RX RX
(j) NH2 NHR N
OH¯ OH¯ R
2º amine 3º amine
Cl NHCH3
NO2 NO2
OH¯
+ CH3NH 2
NO2 NO2
2º amine
Some other methods are very similar to that used for aliphatic amines.
Properties
Physical
• Colourless liquid/solids, but due to air oxidation, they turn brown.
NH2 O
air
colourless O
brown
• Slightly soluble in water (polar solvent) but highly soluble in benzene and other organic solvents.
• High b.p. due to intermolecular H-bonding. N, N-dimethyl aniline hs lower b.p. due to lack of H-
bonding but molecular weight is also important affecting b.p.
CH3
no intermolecular
N: H-bonding possibl
CH3
H
intermolecular
H – N -------H – N --------H – N -------- H-bonding in aniline
H H
• Para-substituted aniline, being the most symmetric, have the highest melting points. Thus p-toluidine is
solid at room temperature while o-toluidines are liquids.
Relations of the –NH2 group

(a) Methylation (Alkylation)
NH2 + CH3I OH¯ NHCH3
CH3
OH¯ CH3I 
N – CH3 N – CH3 I
CH3I
CH3 CH3
quaternary ammonium salts
(b) Acylation
NH2 + CH3COCl NHCOCH3

N-acetyl aniline
(acetanilide)
Acetyl group deactivates – NH2 group, whenever aniline is subjected to nitration, acetylation is neces-
sary to protect the ring from being oxidised.
(c) Sulphonylation
NH2 + SO2Cl NHSO2
benzene sulphonyl N-phenyl

chloride benzene sulphonamide
(Hinsberg reagent) (soluble in alkali)
2º amine also reacts but the product is insoluble in alkali. This provides a method (called Hinsberg
method) of separation of mixture of 1º, 2º and 3º amines.
(d) Oxidation
K2Cr2O7/H2SO4
NH2 O O
p-benzoquinone
NH2 NO NO2
Caro's acid dil. HNO 3

H2SO5
NO2 NO2 NO2
p-nitro p-nitroso p-dinitrobenzene
aniline nitrobenzene
(e) Reaction with H NO 2

1º amines form diazonium salts at low temperature (273–278 K). A reaction in which – NH2 group is
converted into diazo group (– N  N) is called diazotisation. Diazonium salts are stable in cold aqueous
solution.
273 K
NaNO 2 + HCl HNO 2 + NaCl
273 K +
NH2 + HCl NH3 Cl¯
+ 273 K 
NH3 + HNO2 N  NCl¯
benzene diazonium
chloride
Aniline can be converted into so many other compounds through the formation of diazonium salts.
+ H2O, 
N2 Cl¯ OH + N2 + HCl
H3PO2 + H2O + H3PO3 + HCl
CuCl + HCl Cl + N 2
(Sandymeyer)
CuBr + HBr Br + N2
(Sandymeyer)
Cu,  Cl + N2
(Gattermann)
CaCN + HCN CN + N2
KI I + N2 + KCl
HBF 4 +
N 2 BF4¯ F + N2 + BF 3

(Belzschimen)
NaNO2/Cu
NO2
+ N2 + NaCl + H2O
NaOH
diphenyl
NH2
N=N NH2
p-amino azobenzene
(dye)
More reactions are given in sec. 16.8 (diazonium salts)
2º amines form nitrosamine (yellow oily liquid) which is stable at room temperature. However on reac-
tion with HCl in ether and alcohol – NO group migrates to para-position (Fischer-Hepp)
HCl, ether/C2H5OH
NH + HNO2 N – NO ON NHCH3
CH3 CH3
p-nitroso-N-methyl aniline
3º amines form p-nitroso derivatives :
H3C CH3 H3C CH3 CH3 CH3

N
N N
+ HNO2 HCl + H2O
NO NO
(strongly p-activating) p-nitroso,
N, N- dimethyl aniline
N(CH3)2 N(CH3)2 N (CH3)2

+
NO
 H NO
Hydrolysis of p-nitroso derivative gives 2º amines :
H3C NaOH H3C NH

N NO + H2O ON OH +
H3C H3C
p-nitrosophenol 2º amine
This provides a path of the preparation of 2º amines :
 +
NH 2 + K NH¯K + 1/2 H 2
This represent acidic nature of aniline. Hypochlorous acid also reacts with aniline in which active H is
replaced. :
NH 2 + HOCl NHCl + H 2O
N–Chloroaniline
Electrophilic substitution in benzene nucleus

– NH2 group is o, -p directing and activating group.
NH2 NH2 NH2 NH2 NH2
 
Paraderivative


+
NH2
¯ ¯
Electrophile will attach at o & p positions.
¯
Hence, – NH2 group activatives benzene nucleus for ortho and para-electrophilic attack.

NH2 NH2 NH2
H + Y
+ Y Y
–H
(resonance stablised -complex)
(a) Bromination
NH2 NH2
Br Br
+ 3Br2 (aq) + 3HBr2
Br
–NH2 group is greatly activating group hence reaction takes place rapidly. However if ring is deacti-
vated by acetylation, o-and p-iosmers are obtained.
NH2 NHCOCH3 NHCOCH3 NH2

CH3COCl Br2 Br Br
KOH/C2H5OH, 
acetylation +p- + p-
acetanilide o-
(b) Nitration
Direct nitration of aniline with nitric acid gives a complex mixture of mono-,di-and tri-nitro compounds
and oxidation products. If –NH2 group is protected by acetylation and then nitrated, p-isomer is the
main product.
NH2 NHCOCH3 NHCOCH3 NH2

CH3COCl HNO3 NaOH/
NO2 NO2
p-nitroaniline
(c) Sulphonation
 
NH2 NH3HSO4 NHSO3H NH2
H2SO4,   rearrangement
–H2O
SO3H
p-amino benzene sulphonic acid
(sulphanilic acid)
Like antranilic acid, sulphanilic acid also exists as Zwitter ion due to internal neutralisation.
NH2 NH3
SO3H SO3
Zwitter ion
(dipolar ion)
Distinction between Aliphatic and Aromatic Amines
S.No. Test NH2 CH3NH2
1. Diazotisation Diazonium salt is formed – NH is replaced by – OH

+
(reaction with HNO2) N2
which forms azo dye with
phenolic compounds.
2. SE can be halogenated, no
sulphonated, nitrated.
3. Basic nature less basic than CH3NH2, NH3 more basic than NH3
Phenolic compounds
Phenols are the compounds of the general formula ArOH, where, Ar is phenyl or substituted phenyl.
Phenols differs from alcohols in having the –OH group attached directly to an aromatic ring.
OH OH OH OH OH
CH3 OH COOH
OH
phenol o-cresol catechol salicylic acid resorcinol
Source
• From Cumene (Isopropyl benzene)
AlCl3
+ CH3CH2CH2Cl CHCH3
CH3
(Cumene)
AlCl3 O2 air
+ CH3CH = CH2
OH CH3
O
H2O, H+
CH3CCH3 + C – O – OH
CH3
acetone phenol cumene hydroperoxide

• Hydrolysis of Diazonium salts
N2+ HSO4¯ OH
H2O, H , +
+ N2
Cl Cl
Diazonium salts are obtained from aniline and its derivatives by a process called diazotisation.
NH2 N2Cl OH
NaOH2 + HCl H , H2O, 
+
+ N2 + HCl
273 K
CH3 CH3 CH3
m-toluidine
• Alkali Fusion of Benzene Sulphonic Acid salts

SO3Na OH ONa
573 K NaOH
+ NaOH
H+
CH3 CH3 CH3
• Hydrolysis of Aryl Halides
Halogen atom attached to benzene nucleus does not give SN 2 reaction since C–X bond is stable due to
resonance. However, in presence of electron withdrawing group in o- and p-positions, SN reaction is
favoured and phenolic compounds are formed.
Cl OH
NaOH
no reaction (Dow's process)
high, temp, pressure
Cl OH ONa
NO2 NO2 NaOH NO2
NaOH
SN HCl
Cl OH
NO2 NO2
(i) NaOH
(ii) HCl
NO2 NO2
• Distillation of Phenolic Acids

OH OH ONa OH
COOH +
NaOH (CaOH) NaOH H

Salicylic acid
• Oxidation of Grignard Reagent

MgBr
MgBr O2MgBr O2MgBr OH
+
O2 H3O
2
MIDDLE OIL OF COAL-TAR DISTILLATION
Middle oil of coal-tar distillation has naphthalene and phenolic compounds. Phenolic compounds are
isolated in following step :
Step-I : Middle oil is washed with H2SO4. It dissolves basic impurities like pyridine (base).
Step-I : Excessive cooling separates naphthalene (a low melting solid)
Step-III : Filtrate of step II is treated with aqueous NaOH when phenols dissolves as phenoxides.
Carbon dioxide is then blown through the solution to liberate phenols.
CO2, H2 O
OH + NaOH ONa + H 2O OH + Na 2CO 2
Step-IV : Drude phenol (of step III) is subjected to fractional distillation.
450 K phenol
Crude fractional 463 – 476 K o, m, p-cresols
phenols distillation
484 – 508 K xylo(hydroxy xylenes)
Properties
Physical
• Simplest phenols are liquids or low-melting solids.
• They are capable of forming intermolecular H-bonding among themselves and with water. Thus,
– they have high b.p.
– they are soluble in water.
 
+ –
 
+ –
H – O ---- H+ – O– ----H – O ----- H+ – O– -----

   
(intermolecular H-bonding among phenol molecules)
H H
+ – + + – +
H – O ---- H – O– ----H – O ----- H – O– -----
 
(crossed intermolecular H-bonding between water and phenol molecules)
– due to intermolecular H-bonding and high dipole moment, m.p. and b.p. of phenol are much higher
than that of hydrocarbon of comparable molecular weights.
Solute mol. wt. b.p. m.p.

phenol 94 g mol–1 455 K 314 K
toulene 92 g mol–1 384 K 178 K
Comparison of properties of nitrophenols
Isomer b.p. at 760 mm Solubility g/100 g
o-nitrophenol 373 K 0.2 volatile in steam

p-nitrophenol decomposes 1.69 non-volatile in stem
m-nitrophenol 467 K 1.35 non-volatile in steam
From the above table , it is clear that o-nitrophenol has much lower b.p. and much lower solubility in
water than its isomer and is only steam-volatile.
– m and p-isomer have high b.p. because of intermolecular H-bonding and high solubility in water is
again due to crossed intermolecular H-bonding with H2O.
o-isomer has intramolecular H-bonding due to which association with different molecules decreases
hence, b.p. is low giving volatile character to it and also H-bonding with H2O molecules is not possible
which makes it water soluble to a very small extent.
– Steam distillation depends upon a substance having an appreciable vapour pressure at the b.p. of
water , by lowering the v.p., intermolecular hydrogen bonding inhibits steam distillation of the m-and
p-isomer.
O O ----- H – O
N
-----H – O N
O O
intermolecular hydrogen bonding in p-nitrophenol molecules
O H O
N O C H
O H H
intramolecular hydrogen bonding chelation in
in o-nitrophenol (chelation) o-hydroxybenzaldehyde
FORMATION OF COMPLEXES WITH FeCl3
Phenols form coloured iron complexes when related with neutral FeCl3 solution. The formation of iron
complexes is attributed to the existence of keto-enol tautomerism in phenols. Phenol predominantly
exists in enolic form, hence colour formation is used to identify phenols.
OH O
enol keto
Ph–OH + FeCl3  Fe(OPh)3 + 3HCl
Other Reaction of –OH Groups

OH
+ PCl5  Cl + POCl3 + HCl
OH ONa OR
NaOH RX
SN
This is called Williumson’s synthesis. The phenoxide ion is a nucleophile and will replace halogen of the
alkyl halide.
OH + CH 2N 2 OCH3 + N2
anisole
O O
base
OH + CH3CCl OCCH3
or
(CH2CO)2O phenyl acetate
O O
OH + CCl OC
phenyl benzoate
OH O
CrO2Cl2
+ H2O
oxidation
O
p-benzoquinone
(or quinone)
OH O
+ 2 AgOH + 2Ag + 2H2O
OH O
quinol quinone
ELECTROPHILIC SUBSTITUTION IN BENZENE NUCLEUS
–OH group is o- and p-directing and activating group for SE reactions.
O–H  O–H O–H O–H O–H

 
+
OH
Eu+ (electrophile) can attack at o- and
–
– p-sites hence –OH group is o- and
p- directing and activating group

–
OH OH  OH OH OH
+ H Eu
+Eu Eu and and
+
–H
H Eu o- Eu
p-
stable by resonance
(-complex)
HALOGENATION
With excess of Br2 solution :

Br2 + Br2  Br+ + Br3¯
OH OH
Br Br
+ 3Br2
Br
2, 4, 6-tribromophenol
OH OH OH
Br
CS2 or CHCl3
+ Br2 +
273 K
Br
o-bromophenol p-bromophenol
(main)
In presence of NaOH, phenoxide ion is formed which is more reactive than phenol towards electrophilic
aromatic substitution.
 O 
OH O  O O
NaOH Br Br
Br2 Br2
H2O + Br – Br
OH¯
Br H Br
Br
-complex
(neutral)
• Sulphonation
H2SO4 + H2SO3  SO3H+ + HSO4¯ + H2O
OH OH OH
SO3H
+ SO3H+ +
SO3H
o- p-
phenol sulphonic acid
At room temperature , ortho-isomer while at 373 K the para-isomer is the main product.
• Nitration
–OH group is activating group, hence, nitration is possible with dil. HNO3.
HNO3 + HNO3  NO2+ + NO3¯ + H2O
OH OH OH
NO2
+
CHCl3
+ NO2 +
288 K
NO2
o- p-
nitrophenol
HNO3 is oxidising agent and may lead to cleavage of benzene ring hence, further nitration is done
carefully. However ring can be deactivated by sulphonation and then nitration will give picric acid in
better yield.
OH OH OH
SO3H O2N NO2
HNO3
+ H2SO4
SO3H NO2
2, 4, 6-trinitrophenol
(picric acid)
• Nitrosation
HNO2 + H2SO4  NO+ HSO4¯ + H2O
OH OH OH
NO
+
+ NO +
NO2
o- p-
nitrosophenol (90%)
Nitrosophenol can be oxidised to – NO2 by HNO3; this provides a path of preparing nitrophenol.
OH OH
NO NO2
HNO3
• Alkylation (Friedel-Crafts Reaction)
OH ONa ONa OH
CH3I CH3 H
+ CH3
NaOH
benzene AlCl3
o- and p- o- cresol
CH3 CH3
70% H2SO4
OH + CH3 – C – OH AlCl3 H3C – C OH + H2O
CH3 CH3
p-tert-butylphenol
•Acylation (Friedel-Crafts Reaction)
OH OH
O
AlCl3 COCH3
+ CH3CCl and p-
o-acetylphenol

Intermediate of this reaction is CH3C = O (acylium ion).
• Fries rearrangement
When esters or phenols are heated withAlCl3, the acyl group migrates from the phenolic oxygen to an
ortho or para-position of the ring thus, yielding a ketone. This reaction is called the Fries rearrangement
and appears to involve generation of an acylium ion, RCO+, which then attack the ring as in ordinary
Friedel-Cracft acylation.
O
OH O– CC2H5 OH O
C2H5COCl AlCl3 CC2H5
CS2 + p-isomer (non volatile)
o-hydroxy phenyl
ethyl ketone (volatile in steam)
• Claisen rearrangement
OCH2CH = CH 2 OH
473 K CH2CH = CH2
(diphenyl ether)
allyphenyl o-allyl
ether phenol
This is the arrangement of allyl ethers to allyl phenols.Allyl group migrates to ortho-position. If ortho-
position is already occupied, para-isomer is obtained.
*
OCH2CH = CH2 OH
H3C CH3 H3 C CH3
473 K
CH2CH = CH2
*
In this Claisen rearrangement, carbon which gets attached to benzene nucleus is vinylic and not allylic.
• Coupling reactions (Azo dye formation)
Phenol reacts with aryl diazonium salts in presence of alkali at low temperature to form form azo dyes.
(i) NaOH
N2Cl + OH + N=N OH
(ii) H 273 K
p-hydroxyazobenzene
HO
(i) NaOH, 330 K
N = N – Cl + H + N=N
(ii) H , 273-278 K
-naphthol (azodye)
• Reimer-Tiemann Reaction
OH OH OH
(i) aq. NaOH, 330K CHO
(a) + CHCl3 (ii) H
+ +
salicyaldehyde CHO
(steam volatile)
A substituted benzal chloride is initially formed, but is hydrolysed bythe alkaline medium.
OH O¯ O¯ OH
CHCl3. OH¯ CHCl2 OH¯ CHO H
+ CHO
OH OH
(i) aq. NaOH,  COOH
(b) + CCl4 +
+ p-
(ii) H
o-
• Kolbe reaction (Carbonation)

Treatment of the salt of a phenol with CO2 under pressure brings about substitution of the carboxyl
group, –COOH, for hydrogen of the ring. This is called Kolbe reaction.
ONa ONa ONa
400 K, 4-7 atm. COONa H+ COOH
+ CO2
salicylic acid
This provides a path of conversion of phenol into hydroxy carboxylic acids. It seems likely that CO2
attaches itself initiallyto phenoxide oxygen rather than to the ring.
O
ONa OCONa OH
COONa

+ CO2
At high temperature (525 – 575 K), p-isomers is obtained.
O OH O¯ OH
O
H COO¯ + COOH
H
+C=O C – O
O O
H-atom attached to the ortho-position combines with phenoxide oxygen.
Salicylic acid is used to prepare aspirin, salol and picric acid :
OH O O
COH OH OH O O O – CCH3
OH O COH COOH
 CH3CCl
C–O
– CO2
HNO3 aspirin
–CO2
phenyl salicylate (salol)
OH
O2N NO2
NO2
• Gattermann Reaction (Formylation)

OH OH
ZnCl2 CHO
+ HCN + HCl +
H3O
This reaction is used to prepare aldehyde when activating groups like –OH, –NH2 are present.
ZnCl2 
HCN + HCl  Cl – CH = NH CH = NH + ZnCl3¯

OH OH OH OH
 H CH = NH H O+ CHO
CH = NH 3
CH = NH
• Condensation Reaction
(a) Condensation of phenol with HCHO in presence of acid forms bakelite.
OH OH OH OH OH
+ CH2OH + –CH2 CH2 CH2 CH2–
H HCHO/H
+ HCHO + p-
o-hydroxy CH2 CH2 CH2
benzyl alcohol
bakelite
(b) Condensation of phenol with phthalic acid in presence of concentration H2SO4 forms phenolphthalein
(an indicator) which gives pink colour with NaOH (phthalein test of dibasic acid)
O O O
C – OH C conc. H2SO4 C
 O

C – OH C C
O O O
phthalic acid
H H
OH OH
OH OH phenolphthalein
OH
S.No. Test CH3CH2OH
1. Neutral FeCl3 violet colour no reaction

2. Azo dye test with benzene diazonium chloride is no dye formation
formed
N = N – Cl + OH
NaOH, 273 K
N=N OH
3. Phthalein test is given no given

4. Litmus test turns blue no change
5. Iodoform test not given is given
• Sandymeyer Reaction
Nucleophiles such as CN¯, Cl¯ etc., replace the diazonium group if appropriate cuprous salt is added
to the solution containing diazonium salt.
+ CuCl, HCl
N2 Cl¯ Cl¯ + N2
+ CuBr, HCN
N2 Cl¯ Br + N2
+ CuCN, HCN
N2 Cl¯ CN + N2
Sandmeyer reaction involves : CuCl + Cl¯  CuCl2¯
+ CuCl2¯ slow
+
N2 • + N 2 + CuCl
• + CuCl 2 Cl + CuCl
• Gattermann Reaction
CH3 CH3
N2+Br¯ Br
Cu,  + N2
CH3 CH3
+
N2 Cl¯ I
aq. Kl, 
+ N2 + KCl
• Other Replacment Reactions
+ +
N2 Cl¯ N2 Cl¯ NO2
HBr4¯ NaNO2, Cu
+ N2 + NaBF4

CN
KCN, Cu
+ N2 + KCl
CN
K3[Cu(CN)4]
+ N2
OH
H2O, 
+ HCl + N2
H3PO2 + H2O
+ N2 + HCl + H3PO3
or
CH3CH2OH
NH2
NaNH2
+ NaCl + N2
• Gomberg Reaction
+ NaOH
N2 Cl¯ + NO2 NO2 + N2 + NaCl + H2O
+ NaOH
Br N2 Cl¯ + Br + N2 + NaCl + H2 O
• Coupling reaction
Diazonium salts undergo coupling reactions with phenols, naphthols and aromatic amines to form highly
coloured azo-compounds.
Arene diazonium ions acts as weak electrophiles in (aromatic) electrophilic subtitution. The products
have the structure Ar – N = N –Ar, containing the –N = N – azo linkage. Thus products are called azo
compounds and reactions is called diazo coupling. Because diazonium salts are weak electrophiles, they
react only with strongly activated ring (such as phenol, aniline).
N = N – Cl + OH N=N OH
OH¯
CH3
N
CH3 CH 3
+ N=N N
H CH 3
In general :
+
N 2 Cl¯ + G N=N G
(G is strong electron-releasing group : OH, NR2, NHR)
Coupling with benzene substrates occurs preferentially at the less sterically hindered p-position to the
hydroxy or amino group, but if this is blocked, then o-coupling occurs.
+
N2 Cl¯ +
Cl OH
+
H3C H3C N=N
H+ 
NH2 NH3
OH¯
couples does not couple
+
H
O¯ OH
OH¯
couples does not couple
NH2 NH2 NH

3
OH¯ H+ This position is

This position is activated for coupling
activated for coupling
O¯ OH OH
Azo compounds, like alkenes, can exist in cis and trans forms and because of steric strain, the trans-
isomer is more stable than cis-isomer.
N=N N=N
trans-azobenzene cis-azobenzene
Azo compounds bring two substituted aromatic rings into conjugation with an azo group, which is a
strong chromopphore (a functional group absorption of light/colour). Thus most azo compounds are
strongly coloured and they make zo dyes.
O¯
OH
+
O2N NN:+ O2N N=N
para-red
+
O2N NN:+ O O2N N=N OH
COO COO
alizarin yellow
Diazo coupling often takes place in basic solutions since due to deprotponation of the phenolic –OH
group or benzene sulphonic acid and carboxylic groups, activate the aromatic ring for SE reaction.
Common azo dyes have sulphonate/carboxylate groups to enhance solubility of the azo dye in water
and to help bind the dye to the polar surface of common fibres such as cotton and wool.
CARBONYL COMPOUNDS
CHO COCH3 CHO

CHO
OH
benzaldehyde acetophenone salicylaldehy
(oil of bitter almonds) CH3
p-tolualdehyde
O
C
benzophene
Source
• From Toluene
CH3 CHCl2 CHO

Cl2,  H2O, 373 K
CrO3, CH(OOCCH3)2
acetic +
anhydride H2O, H
CH(OCrCl2OH)2
CrO2Cl2(Etard)
• Rosenmund Reaction
COCl CHO
Pd-BaSO4
+ H2 + HCl
catalyst moderator
NO2 NO2
• Acyl chlorides can be reduced to aldehyde bytreating them with lithium tri-teri-butoxyaluminium hydride,
LiAlH(OC(CH3)3]3, at 195 K.
O O
(i) LiAlH[OC(CH 3) 3],
C – Cl CH
diethyl ether, 195 K
(ii) H2O
The reduction is brought by the transfer of a hydride ion from the aluminum atom to the carbonyl carbon
of the acyl chloride. Subsequent hydrolysis frees the aldehyde.
• Reimer-Tiemann reaction is used to prepare phenolic aldehydes
OH OH
CHO

+ CHCl3 + 3KOH (aq) + 3KCl + 2H2O
o-
(and p-)
• Friedel-Crafts Acylation
COC6H5 COCH3
C6H5COCl CH3COCl
AlCl3 AlCl3
(CH3CO)2O, AlCl3
This reaction cannot be used on strongly deactivated aromatic systems.
Gattermann-Koch Reaction
CHO
AlCl3
+ CO + HCl + HCl
CDO
AlCl3
+ CO + DCl + HCl
Thus, HCl (reactant) and HCl (product) are different. H of HCl (reactant) and CO appear in the form of
–CHO in the benzene nucleus. It is confirmed by the fact that using isotopic DCl instead of HCl, would
form –CDO and not –CHO. This reaction also succeeds only with benzene and activated benzene
derivative.
• Gattermann-Aldehyde Synthesis
CHO
AlCl3
+ HCN + HCl + H2O + NH4Cl
• Stephen Reaction
CN CHO
SnCl2/HCl
+
2H /H2O
• Grignard Reagent
MgBr O CHO
HCOC2H5
• Oxidation of Benzyl Chloride
Pb(NO 3)2  O
CH2Cl CH – O – N CHO + HNO2
CrO2Cl2 O
H
• Using Diazonium Salts
 H 2O
N  NCl¯ + CH 2 = CHO CH = NOH CHO
formaldoxime benzaldoxime
MnO2
CH2OH CHO
Properties
Physical
• C6H5CHO is a colourless liquid with smell of bitter almond, sparingly soluble in water but readily in
ehtanol and ether.
• C6H5COCH3 is crystalline solid and is steam volatile; soluble readily in ethanol and ether but sparingly
soluble in water. It produces natural type of sleep when administered orally.
Ortho-quinones, particularly ortho-benzoquinone are less stable than their para-quinone isomers. It is
due to the fact that in ortho-isomer, the C = O bond dipoles are nearly aligned and these have a repulsive
destabilising interaction. In para-isomers, these dipoles are farther apart.
O O
O
o-benzoquinone
(bond dipoles nearly aligned) O
p-benzoquinone
(bond dipoles farther apart)
Chemical
Aromatic carbonyl compounds with following structure
O R=H
CHO = CH3(alkyl)
= C6H5(aryl)
• Conjugation of the carbonyl carbon with the aryl ring reduces the electrophilic reactivity of the carbonyl
carbon atom due to delocalisation of -electrons. Hence, aromatic aldehydes and ketones are less
reactive than aliphatic classes.
• Benzaldehyde, like aliphatic aldehydes, reduces Tollen’s reagent (silver-mirror test). However, it does
not reduce Fehling’s solution. (a distinction from aliphatic class).
• Oxidation
hv
CHO + O2 COOH
Tollen's reagent
• Reduction
CHO + 2H Zn/HCl CH2OH
LiAlH2 Benzyl alcohol
Zn/HCl
2 CHO + 2H CH – CH
OH OH
pinacol (hydrobenzoin)
Zn(Hg) / conc. HCl

COCH3 CH2CH3
Clemmensen
(i) NH2NH2
(ii) glycol/OH¯ (Wolff-Kishner)
PERKIN REACTION
It is the condensation reaction in which aromatic aldehyde is heated with an anhydride of an aliphatic
acid in the presence of sodium salt of the same acid form , -unsaturated acid.
O O
CH3COONa  
CHO + CH3C – O – CCH3 CH = CHCOOH + CH 3COOH
acetic anhydride cinnamic acid
However, with cylic anhydride (succinic anhydride), , -unsaturated acid is formed.
CH2CO CH3COONa  
CHO + O CH = CHCH2COOH
CH2CO
• Reactions of Benzene Nucleus
H–C=O H – C – O H – C – O  H – C --- O H–C–O H – C – O –

Eu+ (electrophile)
  
+

+
will attack m-sites
 
+
CHO CHO CHO

H2SO4 HNO3
SO3 H2SO4
SO3H NO2
Br2/Fe
CHO
Br
EXERCISE - I
Q.1 How many  electron are there in the following species :
(A) 2 (B) 4 (C) 6 (D) 8

Q.2 Benzene is a resonance hybrid mainly of two Kekule structures. Hence:
(A) Half of the molecules correspond to one structure, and half of the second structure
(B)At low temperatures benzene can be separated into two structures
(C) Two structures make equal contribution to resonance hybrid
(D)An individual benzene molecule changes back and forth between two structures
Q.3 Which of the following is not an aromatic compound:
(A) (B) (C) (D)
Q.4 Which of the following group is divalent:

(A) Benzoyl (B) Benzyl (C) Benzal (D) p-Tolyl
Q.5 The number of benzylic hydrogen atoms in ethylbenzene is:
(A) 3 (B) 5 (C) 2 (D) 7
Q.6 Which one of the following is the most basic compound :
(A) C6H5–NH2 (B) C6H5–NHCH3 (C) C6H5–N(CH3)2 (D) C6H5N(C2H5)2
Q.7 Product obtained when benzoyl acetic acid is heated with soda-lime is:
(A) (B) (C) (D)
Q.8 Which of the following is not the property of benzene:

(A) Characteristic smell (B) Inflammable
(C)Addition reactions (D) Colourless
Q.9 Benzyne intermediate is not observed in:
(A) (B) (C) (D)
Q.10 In the reaction of p-chlorotoluene with KNH2 in liquid NH3, the major product is:
(A) o-Toluidine (B) m-Toluidine
(C) p-Toluidine (D) p-Chloroaniline
NaNH
Q.11  
2  A, major product A and reaction R are:
(A) , elimination addition (B) , elimination addition
(C) , cine substitution (D) , addition elimination
Q.12 Which of the following species is expected to have maximum enthalpy in an electrophilic aromatic
substitution reaction?
+ E+    
(I)
(A) Species (II) (B) Species (III) (C) Species (IV) (D) Species (V)
Q.13 For the electrophilic substitution reaction involving nitration, which of the following sequence regarding
the rate of reaction is true?
(A) k C6H 6 > k C6D6 > k C6T6 (B) k C6H 6 < k C6D6 < k C6T6
(C) k C6H 6 = k C6D6 = k C6T6 (D) k C6H 6 > k C6D6 < k C6T6
Q.14 For theelectrophilicsubstitutionreaction involvingsulphonation, whichof thefollowingsequence regarding

the rate of reaction is true?
(A) k C6H 6 > k C6D6 > k C6T6 (B) k C6H 6 < k C6D6 < k C6T6
(C) k C6H 6 = k C6D6 = k C6T6 (D) k C6H 6 > k C6D6 < k C6T6
AlCl
Q.15 + CH 2 CH 2CH 2Cl 3  hydrocarbon (X) major product X is:
|
CH 3
CH 3
|
(A) CH 2CH  CH 3 (B) C  CH 3
| |
CH 3 CH 3
(C) CH2CH2CH2CH3 (D) None is correct

Q.16 In the sulphonation, acetylation and formylation of benzene the group of effective electrophiles would be:
   
(A) SO 3 , CH 3  O, H C O (B) SO 3 , CH 3  C  O, HC O
(C) SO3, CH3CHO, CO + HCl (D) HSO3, CH3CO, HCO
Q.17 Major product of this reaction will be :
CH Cl
3
AlCl3 ,
(A) o-xylene (B) p-xylene (C) Cumene (D) m-xylene
Q.18 For preparing monoalkyl benzene, acylation process is preferred than direct alkylation because
(A) In alkylation, a poisonous gas is evolved
(B) In alkylation, large amount of heat is evolved
(C) In alkylation, polyalkylated product is formed
(D)Alkylation is very costly
Zn  Hg
CH COCl
Q.19 C6H6 3 A    B
AlCl3 HCl
The end product in the above sequence is:

(A) Toluene (B) Ethyl benzene (C) Both the above (D) None
Q.20 C6H6 + A AlCl3  C6H5CONH2

A in the above reaction is:
(A) NH2CONH2 (B) ClCONH2 (C) CH3CONH2 (D) CH2(Cl)CONH2
Q.21 Benzene on reactionwith 'A'forms which on reaction with 'B'forms
'A' and 'B' are:
(A) Zn(Hg) + conc. HCl, (B) , LiAlH4
(C) , NaBH4 (D) , Zn(Hg) + conc. HCl

Q.22 Which of the following carbocations is expected to be most stable?


CH3
(A) (B) (C) (D)
CH3
Q.23 Which of the following carbocations is expected to be most stable?
(A) (B) (C) (D)
Q.24 p-Nitrotoluene on further nitration gives:
(A) (B) (C) (D)
Q.25 Ring nitrationof dimethyl benzene results inthe formation ofonlyone nitro dimethyl benzene. Thedimethyl
benzene is:
(A) (B) (C) (D) None of these
EXERCISE II
Q.1 Which of the following are classified as aromatic?

(A) 1, 2, 3-Triphenylcyclopropenium cation (B) Cyclooctatetraenyl dianion
(C)Azulene (D)Annulene
Q.2 Which aromatic compound is obtained when n-octane undergoes catalytic hydroforming:
(A) ethyl benzene (B) m-Xylene (C) o-Xylene (D) p-Xylene
Q.3 Which of the following reactions of benzene proves the presence of three carbon–carbon double bonds
init:
(A) Formation of a triozonide with ozone
(B) Hydrogenation of benzene to cyclohexane
(C) Formation of C6H6Cl6 by addition of chlorine
(D) Formation of nitrobenzene on heatingbenzene with a mixture of concentrated nitric acid and sulphuric
acid
Q.4 Which of the following can be used in Friedel Crafts reaction to generate electrophile?
(A) (B) CH2=CH–Cl (C) CH3CH2Cl (D) CH2=CH–CH2–Cl
Q.5 The replacement of a hydrogen atom in benzene by alkyl group can be brought about with the following
reagents:
(A)Alkyl chloride andAlCl3 (B)Alkene andAlCl3
(C)Alkanol and alkali (D)Alkanol and acid
Q.6 Benzene reacts with n-propyl chloride in the presence of anhydrousAlCl3 to give predominantly:
(A) n-Propylbenzene (B) Isopropylbenzene
(C) 3-Propyl-1-chlorobenzene (D) Cumene
Q.7 In which of the following reaction t-butylbenzene is formed:

BF . HF
(A) Benzene + iso-butyl chloride,AlCl3 (B) Benzene + (CH3)2C = CH2 3 

(C) Benzene + t-butyl alcohol H2SO

4  (D) Benzene + (CH3)2 C= CH2 AlCl
3 
Q.8 Which of the following does not gives Friedel-Crafts reaction?
(A) (B) (C) (D)
Q.9 The good method for converting benzene into propyl benzene is:
(A) C6H6 + CH3CH2CH2Cl + Anhyd. AlCl3
(B) C6H6 + CH3CH2COCl +Anhyd. AlCl3 and then treatment with Zn/Hg/HCl
(C) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and then treatment with H2 Ni
(D)C6H6 + Anhyd. AlCl3 + cyclopropane
Q.10 The structure of the compound that gives a tribromo derivative on treatment with bromine water is:
CH3
CH3 SO3H COOH
OH
(A) (B) (C) (D)
OH OH
OH
Q.11 Which of the following statements is incorrect for electrophilic substitution.

(A) Ortho-and para-directing groups increase electron density at ortho-and para-positions
(B) Meta-directing groups increase electron density at meta-position
(C) Meta-directing groups decrease electron density at meta-position
(D) Ortho-and para-directing groups decrease electron density at meta-position
Q.12 Which of the following statements is/are not true?

(A)All ortho-para directing groups activates the ring
(B)All ortho-para directing groups except halogens activate the ring
(C) All meta-directing groups have -bond on the atom directly attached to the ring
(D)All meta directing groups are deactivating.
(D) Compound which have maximum resonance (S)
energy
EXERCISE - III
SECTION-A
(JEE ADVANCED Previous Year's Questions)
Q.1 Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of
sodium acetate? [JEE 2005]
—
(A) CH3 CO O N a
(B) CH3 + SO3

(C) CH3 SO 3 N a + CH3COOH
(D) CH3 SO2O. COCH3 + NaOH
AlCl (i ) O / 
Q.2  Cl  CH 2CH 2  CH 3 3  P  
2
 Q  Phenol [JEE 2006]
(ii ) H3O 
The major products P and Q are
(A) and CH3CH2CHO (B) and CH3COCH3
(C) and CH3COCH3 (D) and CH3CH2CHO
Q.3 In the following reaction, [JEE 2007]
conc. HNO
   3  X
conc. H SO 2 4
the structure of the major product 'X' is

O2N
O O
(A) (B)
N NO2 N
H H
O O
N O2N N
(C) (D) H
H
NO2
Q.4 STATEMENT-1 : Bromobenzene upon reaction with Br2 / Fe gives 1, 4-dibromobenzene
as the major product.
STATEMENT-2 : In bromobenzene, the inductive effect of the bromo group is more dominant
than the mesomeric effect in directing the incoming electrophile.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True [JEE 2008]
Q.5 STATEMENT-1 : Aniline on reaction with NaNO2 / HCl at 0°C followed by coupling with -naphthol
gives a dark blue coloured precipitate.
and
STATEMENT-2 : The colour of the compound formed in the reaction of aniline with NaNO2 / HCl at 0°
followed by coupling with -naphthol is due to the extended conjugation.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True [JEE 2008]
Q.6 Match each of the compounds given in Column I with the reaction(s), that they can undergo, given in
Column II. [IIT 2009]
Column I Column II
Br
(A) (P) Nucleophilic substitution
O
(B) OH (Q) Elimination
CHO
(C) (R) Nucleophilic addition
OH
Br
(D) (S) Esterification with acetic anhydride
NO2
(T) Dehydrogenation
OH
Q.7 In the reaction NaOH

 ( aq  the intermediate(s) is(are)
) /
Br2 [JEE 2010]
 
O O O 
O
Br
(A) (B) (C) (D)
Br Br Br Br Br
Q.8 The compounds P, Q and S [JEE 2010]

O
COOH OCH3 ||
C
O
HO H3C
P Q
S
were separately subjected to nitration using HNO3 / H2SO4 mixture. The major product formed in each
case respectively, is
O
COOH OCH 3 C
O
(A) HO H 3C O2 N
NO2 NO2
O
COOH OCH 3 C
O
(B) HO NO2 H 3C NO2
NO2
O NO2
COOH OCH3 C
O
(C) H3C NO2
HO
NO2
O
COOH OCH 3 C
O NO2
(D) HO H3 C NO2
NO2
Q.9 A mongst thecompoundsgiven, theonethat would form abrilliant colored dyeon treatment with NaNO2
in dil. HCl followed by addition to an alkaline solution of -naphthol is [JEE 2011]
(A) (B)
(C) (D)
Q.10 The major product of the following reaction is [JEE 2011]
(A) (B)
(C) (D)
Q.11 Which of the following molecules, in pure from, is (are) unstable at room temperature ? [JEE 2012]
(A) (B) (C) (D)
Q.12 In the following reaction, the product(s) formed is(are) [JEE Advance 2013]
OH
CHCl3
OH— ?
CH3
OH O OH OH
OHC CHO CHO
CH3 H3C CHCl2 H3C CHCl2 CH3

P Q R S
(A) P (Major) (B) Q (Minor) (C) R (Minor) (D) S (Major)
Q.13 The major product(s) of the following reaction is(are) [JEE Advance 2013]
OH
aqueous Br2(3.0 equivalents)
?
SO3H
OH OH OH OH
Br Br Br Br Br
Br Br Br Br Br
SO3H Br Br SO3H
P Q R S
(A) P (B) Q (C) R (D) S
Paragraph for Questions 14 and 15

P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O. On heating, P forms the
cyclic anhydride. Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or
more than one from S, T and U.
COOH COOH COOH
H OH H OH HO H
H OH HO H H OH
COOH COOH COOH
(S) (T) (U)
Q.14 In the following reaction sequences V and W are, respectively [JEE Advance 2013]
H 2 / Ni
Q   V

AlCl3 ( anhydrous ) i ) Zn  Hg / HCl

+ V      (   W
(ii ) H 3PO 4
CH2OH
(A) and (B) and
CH2OH
(V) (W) (V) (W)
HOH2C
(C) and (D) and
CH2OH CH2OH
(V) (W) (V) (W)
Q.15 Compounds formed from P and Q are, respectively [JEEAdvance 2013]
(A) Optically active S and optically active pair (T, U)
(B) Optically inactive S and optically inactive pair (T, U)
(C) Optically active pair ( T, U) and optically active S
(D) Optically inactive pair (T, U) and optically inactive S.
Q.16 The reactivity of compound Z with different halogens under appropriate conditions is given below :
OH mono halo substituted derivative when X 2 = I 2
X2
di halo substituted derivative when X 2 =Br2
C(CH3)3
tri halo substituted derivative when X 2 = Cl2
Z
The observed pattern of electrophilic substitution can be explained by [JEEAdvance 2014]
(A) the steric effect of the halogen
(B) the steric effect of the tert-butyl group
(C) the electronic effect of the phenolic group
(D) the electronic effect of the tert-butyl group
Q.17 For the identification of -naphthol using dye test, it is necessary to use [JEEAdvance 2014]
(A) dichloromethane solution of -naphthol
(B) acidic solution of -naphthol
(C) neutral solution of -naphthol
(D) alkaline solution of -naphthol
Q.18 Match the four starting materials (P, Q, R, S) given in List I with the corresponding reaction schemes
(I, II, III, IV) provided in List II and select the correct answer using the code given below the lists.
List- I List-II [JEEAdvance 2014]
P. H H 1. Scheme I

(i ) KMnO4 , H O ,heat ( ii ) H  ,H 2O
(iii ) SOCl 2 ( iv ) NH3
?          C7 H 6 N 2 O3
OH
Q. 2. Scheme II
OH
(i ) Sn / HCl ( ii ) CH 3COCl (iii ) conc. H 2SO 4
(iv ) HNO3 ( v ) dil.H 2SO 4 , heat ( vi ) HO 
?            C 6 H 6 N 2O 2
NO2
R. 3. Scheme III
(i ) red hot iron ,873 K ( ii ) fu min g HNO3 , H 2SO 4 , heat

? (
iii ) H 2S. NH3 ( iv ) NaNO2 ,H 2SO 4 ( v ) hydrolysis
  C6 H 5 NO3
NO2
S. 4. Scheme IV
CH3
(i ) conc.H 2SO 4 , 60C
? (
ii ) conc.HNO3 ,conc.H 2SO 4 (iii ) dil.H 2SO 4 ,heat
  C 6 H 5 NO 4
Code:
P Q R S P Q R S
(A) 1 4 2 3 (B) 3 1 4 2
(C) 3 4 2 1 (D) 4 1 3 2
Q.19 Among the following, the number of reaction(s) that produce(s) benzaldehyde is :[JEEAdvance 2015]
CHCl2
CO,HCl H 2O
I. Anhydrous AlCl3/ CuCl II. 100°C
COCl CO2Me
H2 DIBAL-H
III Pd-BaSO 4 IV. Toluene,–78°C
H2O
Q.20 The major product U in the following reactions is [JEE Advance 2015]
CH2 = CH – CH3, H+ radical initiator, O 2
T U
high pressure, heat
H H
O O
O H3 C CH 3 O CH2
CH3 O CH2 O H
O H O
(A) (B) (C) (D)
Q.21 In the following reactions, the major product W is [JEE Advance 2015]
OH
NH2 , NaOH
NaNO 2, HCl
0°C
V W
OH
N=N OH N=N
(A) (B)
HO
OH
N=N
(C) N=N (D)
Q.22 The correct statement(s) about the following reaction sequence is(are) [JEEAdvance 2016]
Cumene (C9H12) ( ii  P CHCl
(i ) O2
) H O
   Q (major) + R (minor)
3 / NaOH
Q PhCH
Br S
NaOH
2
(A) R is steam volatile

(B) Q gives dark violet coloration with1% aqueous FeCl3 solution
(C) S gives yellow precipitate with 2, 4-dinitrophenylhydrazine
(D) S gives dark violet coloration with 1 % aqueous FeCl3 solution
Q.23 The product(s) of the following reaction sequence is(are) [JEEAdvance 2016]
NH2
i ) Acetic anhydride/pyridine
     

ii) KBrO3 / HBr
iii ) H 3O , heat
iv ) NaNO 2 / HCl , 273 278 K
v ) Cu/HBr
Br Br Br
Br Br
Br
(A) (B) (C) Br Br (D)
Br
Br Br
Q.24 Among the following, reaction(s) which gives (give) tert-butyl benzene as the major product is (are)
[JEEAdvance 2016]
Br Cl
(A) (B) AlCl3
NaOC2H5
OH
(C) (D) BF3OEt2

H2SO4
Treatment of compound O with KMnO4 / H+ gave P, which on heating with ammonia gave Q. The
compound Q on treatment with Br2/NaOH produced R. On strong heating, Q gave S, which on further
treatment with ethyl 2-bromopropanoate in the presence of KOH followed by acidification, gave a
compound T.
(O)
Q.25 The compound R is [JEEAdvance 2016]
O O O
NH2
Br NHBr
(A) (B) (C) (D) NBr
NH2 Br NHBr
O O O
Q.26 The compound T is [JEEAdvance 2016]

(A) glycine (B) alanine (C) valine (D) serine
Answer Q.27, Q.28 and Q.29 by appropriately matching the information given in the three
columns of the following table. [JEEAdvance 2017]
Columns 1, 2 and 3 contain starting materials, reaction conditions, and type of reactions,
respectively.
Column 1 Column 2 Column 3
(I) Toluene (i) NaOH / Br2 (P) Condensation
(II) Acetophenone (ii)Br2/ h (Q) Carboxylation
(III) Benzaldehyde (iii) (CH3CO)2O/CH3COOK (R) Substitution
(IV) Phenol (iv) NaOH / CO2 (S) Haloform
Q.27 The only CORRECT combination in which the reaction proceeds through radical mechanism is
(A) (II) (iii) (R) (B) (III) (ii) (P) (C) (IV) (i) (Q) (D) (I) (ii) (R)
Q.28 For the synthesis of benzoic acid, the only CORRECT combination is
(A) (III) (iv) (R) (B) (IV) (ii) (P) (C) (II) (i) (S) (D) (I) (iv) (Q)
Q.29 The only CORRECT combination that gives two different carboxylic acids is
(A) (IV) (iii) (Q) (B) (I) (i) (S) (C) (III) (iii) (P) (D) (II) (iv) (R)
Q.30 The major product of the following reaction is [JEEAdvance 2017]
OH
i ) NaNO 2 , HCl, 0C

(    
( ii ) aq.NaOH
NH2
+
ONa OH
(A) (B)
N2Cl Cl
OH
N=N OH
(C) (D)
N=N

The reaction of compound P with CH3MgBr (excess) in (C2H5)2O followed by addition of H2O gives
Q. The compound Q on treatment with H2SO4 at 0°C gives R. The reaction of R with CH3COCl in the
presence of anhydrous AlCl3 in CH2Cl2 followed by treatment with H2O produces compound S.
[Et in compound P is ethyl group] [JEEAdvance 2017]
(H3C)3C CO2Et
Q R S
Q.31 The reactions, Q to R and R to S, are

(A) Dehydration and Friedel-Crafts acylation
(B) Friedel-Crafts alkylation and Friedel-Crafts acylation
(C) Friedel-Crafts alkylation, dehydration and Friedel-Crafts acylation
(D)Aromatic sulfonation and Friedel-Crafts acylation
Q.32 The product S is

HO3S
H3COC (H3C)3 C O CH3
(H3C)3 C H3C CH3
(A) (B)
COCH3
H3C CH3
(H3C)3C COCH3
(H3C)3C CH3
(C) (D)
COCH3
SECTION-B
(JEE Main Previous Year's Questions)
Q.1 Bottles containing C6H5I and C6H5CH2I lost their original labels. They were labelled A and B for
testing. A and B were separately taken in test tubes and boiled with NaOH solution. The end solution
in each tube was made acidic with dilute HNO3 and then some AgNO3 solution was added.
Substance B gave a yellow precipitate. Which one of the following statements is true for this experiment?
(A) B was C6H5I (B) Addition of HNO3 was unnecessary
(C) A was C6H5I (D) A was C6H5CH2I [AIEEE-2003]
Q.2 Which one of the following undergoes reaction with 50% sodium hydroxide solution to give the
corresponding alcohol and acid ? [AIEEE-2004]
(A) Phenol (B) Benzaldehyde (C) Butanal (D) Benzoic acid
Q.3 p–cresol reacts with chloroform in alkaline medium to give the compound A which adds hydrogen
cyanide to form, the compound. B The latter on acidic hydrolysis gives chiral carboxylic acid. The
structure of the carboxylic acid is - [AIEEE-2005]
(A) (B)
(C) (D)
Q.4 Fluorobenzene (C6H5F) can be synthesized in the laboratory - [AIEEE 2006]

(A) from aniline bydiazotisation followed by heating the diazonium salt with HBF4
(B) by direct fluorination of benzene with F2 gas
(C) by reacting bromobenzene with NaF solution
(D) by heating phenol with HF and KF
Q.5 Phenyl magnesium bromide reacts with methanol to give - [AIEEE 2006]
(A) a mixture of benzene and Mg(OMe) Br (B) a mixture of toluene and Mg(OH)Br
(C) a mixture of phenol and Mg(Me)Br (D) a mixture of anisole and Mg(OH) Br
– +
OH O Na
Q.6 + CHCl3 + NaOH
CHO
The electrophile involved in the above reaction is - [AIEEE 2006]
Θ
(A) dichlorocarbene ( :CCl2) (B) trichloromethyl anion ( CCl3)
 
(C) formyl cation (CHO) (D) dichloromethyl cation (CHCl2)
Q.7 The structure of the compound that gives a tribromo derivative on treatment with bromine water is -
[AIEEE 2006]
CH2OH CH3 CH3 CH3
OH
(A) (B) (C) (D)
OH
OH
Q.8 The reaction of toluene with Cl2 in presence of FeCl3 gives predominantly- [AIEEE 2007]
(A) benzoyl chloride (B) benzyl chloride
(C) o-andp-chlorotoluene (D) m-chlorotoluene
Q.9 Phenol, when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid,
gives- [AIEEE 2008]
(A) o-nitrophenol (B) p-nitrophenol (C) nitrobenzene (D) 2,4,6-trinitrobenzene
Q.10 Toluene is nitrated and the resulting product is reduced with tin and hydrochloric acid. The product so
obtained is diazotised and then heated with cuprous bromide. The reaction mixture so formed contains-
[AIEEE 2008]
(A) mixture of o– and p-dibromobenzenes (B) mixture of o- and p-bromoanilines
(C) mixture of o- and m-bromotoluenes (D) mixture of o- and p-bromotoluenes
Q.11 The major product obtained on interaction of phenol with sodium hydroxide and carbon
dioxide is - [AIEEE 2009]
(A) salicylaldehyde (B) salicyclic acid (C) phthalic acid (D) benzoic acid
Q.12 In the chemical reactions
NaNO
  2  A HBF
4  B
HCl, 278 K
the compound 'A' and 'B' respectively are : [AIEEE-2010]

(A) Benzene diazonium chloride and fluorobenzene (B) Nitrobenzene and chlorobenzene
(C) Nitrobenzene and fluorobenzene (D) Phenol and benzene
Q.13 Phenol is heated with a solution of mixture of KBr and KBrO3. The major product obtained in the above
reaction is : [AIEEE-2011]
(A) 2-Bromopheonol (B) 3-Bromopheonol (C) 4-Bromopheonol (D) 2, 4, 6-Tribromophenol
Q.14 Which of the following reagents may be used to distinguish between phenol and benzoic acid ?
[AIEEE-2011]
(A) Aqueous NaOH (B) Tollen's reagent (C) Molisch reagent (D) Neutral FeCl3
Q.15 Ortho-Nitrophenol is less soluble in water than p- and m-Nitrophenols because : [AIEEE-2012]
(A) o-Nitrophenol shows intermolecular H-bonding
(B) Melting point of o-Nitrophenol is lower than those of m-and p-isomers.
(C) o-Nitrophenol is more volatile in steam than those of m-and p-isomers.
(D) o-Nitrophenol shows intramolecular H-bonding
Q.16 Aspirin is known as : [AIEEE-2012]
(A)Acetyl salicylate (B) Methyl salicylic acid
(C)Acetyl salicylic acid (D) Phenyl salicylate
Q.17 What is DDT among the following : [AIEEE-2012]
(A) Biodegradable pollutant (B) Non-biodegradable pollutant
(C) Greenhouse gas (D)Afertilizer
Q.18 Compound (A), C8H9Br, gives a white precipitate when warmed with alcoholicAgNO3. Oxidation of
(A) gives an acid (B), C8H6O4. (B) easily forms anhydride on heating. Identify the compound (A).
CH2Br CH2Br
C2H5 CH 2Br
(A) (B) (C) (D)
Br CH 3 CH3
CH3
[JEE Main-2013]
Q.19 A solution of (–) – 1–chloro –1– phenylethane on toluene racemises slowly in the presence of a small
amount of SbCl5 due to the formation of: : [JEE Main-2013]
(A) carbene (B) carbocation (C) free radical (D) carbanion
Q.20 Sodium phenoxide when heated with CO2 under pressure at 125°C yields a product which on acetylation
produces C. [JEE Main 2014]
ONa 125° H+
+ CO2 5 atm B Ac O C
2
The major product C would be :

OH
OH
COCH3
(A) (B) COOCH3
COCH3
OCOCH3 OCOCH3
(C) (D) COOH

COOH
Q.21 In the reaction : [JEE Main 2015]

NH2
NaNO
 2/ HCl
 D CuCN
 / 
KCN
 E + N the product E is :
0 5 º C  2
CH3
CN CH3
(A) (B)
CH3
COOH
(C) (D) H3C CH3
CH3
Q.22 In the following sequence of reactions : [JEE Main 2015]
 4  A 2  B BaSO
 C
SOCl H 2 / Pd
Toluene KMnO
4
the product C is :
(A) C6H5CH2OH (B) C6H5CHO (C) C6H5COOH (D) C6H5CH3
Q.23 Which of the following compounds will form significant amount of meta product during mono-nitration
reaction? [JEE Main 2017]
OCOCH3 NH2
(A) (B)
NHCOCH3 OH
(C) (D)
ANSWER KEY
EXERCISE - I
Q.1 C Q.2 C Q.3 B Q.4 C Q.5 C Q.6 D Q.7 A
Q.8 C Q.9 B Q.10 B Q.11 A Q.12 A Q.13 C Q.14 A
Q.15 D Q.16 B Q.17 D Q.18 C Q.19 B Q.20 B Q.21 D
Q.22 B Q.23 D Q.24 A Q.25 C
EXERCISE II
Q.1 ABC Q.2 AC Q.3 ABC Q.4 CD Q.5 ABD
Q.6 BD Q.7 ABCD Q.8 BCD Q.9 BD Q.10 BCD
Q.11 BCD Q.12 ABC
EXERCISE - III
SECTION-A
Q.1 C Q.2 C Q.3 B Q.4 C Q.5 D
Q.6 (A) ,Q,T (B) P,S,T (C) R,S (D) P Q.7 ABC Q.8 C Q.9 C
Q.10 A Q.11 BC Q.12 BD Q.13 B Q.14 A
Q.15 B Q.16 ABC Q.17 D Q.18 C Q.19 4
Q.20 B Q.21 A Q.22 BC Q.23 B Q.24 BCD
Q.25 A Q.26 B Q.27 D Q.28 C Q.29 C
Q.30 C Q.31 C Q.32 C
SECTION-B
Q.1 C Q.2 B Q.3 A Q.4 A Q.5 A
Q.6 A Q.7 D Q.8 C Q.9 D Q.10 D
Q.11 B Q.12 A Q.13 D Q.14 D Q.15 D
Q.16 C Q.17 B Q.18 C Q.19 B Q.20 D
Q.21 A Q.22 B Q.23 B

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ORGANIC CHEMISTRY

TARGET JEE 2018

Fraction Temperature Main constituents

[i] Discoverer : Michael Faraday [ii] C–hybridisation : sp2

[ix] Number of angles of 120º : 18

Localized –orbital Localized –orbital

Methods of Preparation of Benzene :

ELECTROPHILIC AROMATIC SUBSTITUTION (EAS)

As a result, the characteristic reaction of benzene is electrophilic aromatic substitution - a hydrogen

Product is not aromatic Product is aromatic

THE GENERAL MECHANISM OF EAS

EAS reactions occur via a two steps mechanism.

Step 1. Addition of the electrophile

Step 2. Loss of a proton to reform the aromatic ring

Problem : Compare rate of nitration among C6H6, C6D6 and C6T6.

The introduction of halo (–X) group on benzene known as halogenation of benzene

Mechanisms for Bromination

Mechanisms for Chlorination

Mechanisms for Iodination

The electrophile required for halogenation reaction is halonium ion ( X )

Benzene sulphonic acid

Ortho para directors Meta directors

CH3 CH3 CH3 CH3 CH= CH2 CH(CH3)2

(b) High temperature cracking

3CH  CH red-hot tube

red-hot tube (o, p-also)

(d) Alkyl benzene synthesis

(e) Friedel-Crafts reaction

(f) Decarboxylation of Aromatic acids

(h) Deoxygenation of Phenols

(i) Reduction of Diazonium salts

(j) Desulphonation of sulphonic acids

Mechanisms of the above reactions have been given in further section.

1. All meta-directing groups are deactivating groups;

(substituents donates electrons by resonance into the benzene ring)

(substituents donates electrons aways from the benzene ring)

(b) Addition of Halogen

CH3 CH(OOCCH3)2 CHO

CH3 CH3 CCl3

, CH3Cl, AlCl3 3Cl2

NBS, benzoyl peroxide

(NBS is N-bromo succinimide)

DIRECTING INFLUENCE AS DECIDED BY ELECTRON DENSITY

1 to V are different resonance structures and VI resonance hybrid structure.

In this case nucleophilic attack at electron-rich ortho and para-sites is favoured.

ANAMALOUS BEHAVIOUR OF HALOGEN SUBSTITUENT

– X(F, Cl, Br, I) is o–, p-directing but is deactivating group.

electron displacement overall result; o–,

Thus, hyperconjugation helps in increasing-density at o-and p-sites in case of alkyl groups.

Orientation and Synthesis

Orientation in Disubstituted benzene

NO2 ortho w.r.t. – CH3

Problems may arise in the following cases :

CH3 Weakly activating

weakly activating OH OH CH3

CH3 CH3 CH3

H+ + HNO3 + 1/2 I2  I+ + NO2 + H2O

Diazonium salts are converted to halogen compounds :

CuCl Cl + H 2O (Raschig process)

CH3 CH2Cl CHCl2 CCl3

stable benzyl free radical

In presence of an activating group – OH or – NH2, side chain halogenation is difficult :